4-halo-2-butynayl n-(1, 2, 4-triazol-3-yl)-carbamates



United States Pa p w 3,132,150 Patented May 5,, .1964

4-HALO-2-BUTYNYL N-(1,2,4-TRIAZL-3-YL)- C'AMATES Thomas R. Hopkins and Joe .W. Pullen, Overland Park,

Kans., assignors to Spencer Chemical Company, Kansas City, Mo., acorporation of Missouri No Drawing. Original application Aug. 24, 1960, Ser. No. 51,510. Divided and this application Oct. 6, 1961,

Ser, No. 143,285 Y 2 (Ilaims. (Cl. 260-308) This invention relates to chemical compounds having, herbicidal properties. More particularly, this invention is concerned with novel 4 -halo-2-butynyl carbamates having herbicidal activity.

This application is a continuation-in-part of our copending application Serial No. 786,674, filed January 14,

' 1959, and is a divisional application of our copending application Serial No. 51,510, filed August 2.4, 1960.

According to the present invention there are provided novel 4-halo-2-butynyl N-allyl N (3-halophenyl)carbamates and novel 4-halo 2 butynyl N-( 1,2,4-triazol-3-yl) carbamate s.

Representative of the '4-halo-2-butynyl N-allyl N (3- halophenyl)carbamates is 4-chloro 2 butynyl N-allyl- N- (3-chlorophenyl)carbamate which has been found to have rather selective post-emergence herbicidal or plant growth regulating properties against millet, flax and oats. The activity of this compound was evaluated according to a standard foliage herbicide screen as follows:

A water suspension of the compound was prepared by adding to 0.4 g. of the compound in a mortar, 4 drops of Emulphor EL (a polyoxyethylated vegetable oil) and the mixture was ground together in the mortar. A few drops of water were added and when the mixture was workable, additional water was added to bring the volume up to 20 ml. 20 ml. of a kerosene emulsion (19% kerosene and 1% Emulphor EL in water).was added. Oats (Avemz sativa), wheat, peas, radish, flax, alfalfa, millet,

' sugar beets, and Bonnie Best tomatoes were planted in 40 4" clay pots. When the plants had reached a suitable growth (3"8") they were sprayed With the above water emulsion at the rate of 5 lbs. of the carbamate per acre at a spray volume of 60 gallons of water per acre. Two weeks after the application, the plants were observed and the results of treatment recorded as in Table 1. 45

TABLE 1 1 The scale of Table 1 was used for evaluation.

4-chloro-2-butynyl N-(1,2,4 triazol 3 yl)carbamate was evaluated for herbicidal activity using the standard 'post emergence herbicide screening test described above.

The application rate was 5 lb./acre. The following results were obtained:

TABLE 3 Oats Wheat Soy- Rad- Flax Millet Alfalfa Tomato Sugar beans ish Beets ,03 C4 ICN2 O2 02 C4 C3 C1 0N1 Evidence indicates that the 'carbamates of this inven- I tion have herbicidal activity when applied at the rate of about 0.10 to about 25 pounds/acre; however, a rate of 0.5 to lO'ponnds/acre is advisably employed inmost 1 cases. r

The compounds can be applied as powders or in liquid carriers as solutions ordispersions. Sticking agents and wetting agents and other conventional adjuvants can be employed as advisable.

The following examples illustrate the preparation of the novel compounds of this invention.

Example I 4-CHLO'RO-2-BUTYNYL N-ALLYL-N-(S-OHLOROPHENYL) CARBAMATE To a stirred mixture of 276.1 g. (1.65 moles) of N-allyl-3-chloroaniline, 1.65 moles of pyridine and 1000 ml. of benzene was added 275.5 g. (1.65 moles) of 4-chloro-2-butynyl'chlorocarbonate, dropwise at 1520 (3., over a period of about 1 hour. Stirring was continued 1 Efiects e on Various Crops (Application Rate 5 lbs/A.)

Compound Oats Wheat Peas Rad- Flax Millet Alfalfa ish Tomato Sugar Beets N-allylderivative G2 7 0 0 G3 4 O a Key to ratings: 0 chlorosis; G =inhibition of growth; N =necrosis; 0 =no efiect; 1 =slight (less than 25% affected foliage); 2=moderate (25%70% affected foliage); 3=severe (71 l 99% afiected foliage); 4=dead plants Additional herbicidal tests were run with 4-chloro-2- butynyl N-allyl- N (3-chlorophenyl)carbamate with results obtained reported in Table 2.

p at ambient temperature for about 2 hours. One liter of water was added to the mixture and, after stirring, the organic layer was separated and washed with dilute hydro- 3 chloricacid, with'water and then dried over anhydrous magnesium sulfate. The solvent was re'movedhy'distilla tion under reduced pressure (Water aspirator) to give 4-cl1loro-2-butyny1 N allyl -'N (3 chlorophenyl)carbamate, which has a boiling point of 159 C./0.45 mm; N 1.5566. 7

Example 2 4-CHLORO-2-BUIYNYL N-(1,2,4-TRIAZOL-3-YL) ,CARBAMATE I V 4 crystalline material was dissoived in hot acetone, the ace tone solution filtered and then diluted with n-hexane. The solution was chilled, crystallizing the product, which was removed by filtration. A yield of 46 g. (43%) of the carbamate, MP. 157 C. With decomposition, was obtained. 1

Various changes and modifications of the invention can be made and, to the extent that such variations incorporate the spirit of this invention, they are intended to be included Within the scope of the appended claims.

What is claimed is:

1 4-,ha1o-2-butynyl N-(1,2,4 triaz01-3-yl)carbamate.

2. 4-ch1oro-2-butynyl N-( 1,2,4-triazol-3-yl) carbamate.

References Cited in the file of this patent UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3 132 150 May 5 1964 Thomas R. Hopkins et a1 It is hereby certified that error appears in the above numbered pt ent requiring correction and that the said Letters Patent should read as corrected below.

Column 2 TABLE 2, third column, line 1 thereof for "G" read G3 column 4 line l9 for "Kingsberg" read Klingsberg Signed and sealed this 8th day of September 1964,

( SEAL) I i Attest;

l ERNEST W. SWIDER' I EDWARD J. BRENNER I Attesting Officer Commissioner of Patents I 

1. 4-HALO-2-BUTYNYL N-(1,2,4-TRIAZOL-3-YL)CARBAMATE. 